三维多孔碳限域的磷化钴电催化剂用于高效的锌-空气电池和水分解

doi:10.1016/S1872-2067(21)64047-0

催化学报 ›› 2022, Vol. 43 ›› Issue (12): 3107-3115.DOI: 10.1016/S1872-2067(21)64047-0

三维多孔碳限域的磷化钴电催化剂用于高效的锌-空气电池和水分解

舒欣欣^a^,^†, 杨茅茂^a^,^†, 刘苗苗^a, 王怀生^b, 张进涛^a^,^*()

^a山东大学化学与化工学院, 胶体与界面化学教育部重点实验室, 山东济南250100
^b聊城大学化学与化工学院, 山东聊城252059

收稿日期:2022-01-21 接受日期:2022-02-22 出版日期:2022-12-18 发布日期:2022-10-18
通讯作者: 张进涛
作者简介:第一联系人：
^†共同第一作者.
基金资助:
国家自然科学基金(22175108);山东省杰青青年基金(ZR2020JQ09);山东省泰山学者计划(tsqn20161004);山东省高校青年学者创新团队项目(2019KJC025)

In-situ formation of cobalt phosphide nanoparticles confined in three-dimensional porous carbon for high-performing zinc-air battery and water splitting

Xinxin Shu^a^,^†, Maomao Yang^a^,^†, Miaomiao Liu^a, Huaisheng Wang^b, Jintao Zhang^a^,^*()

^aKey Laboratory for Colloid and Interface Chemistry of State Education Ministry, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, Shandong, China
^bSchool of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, Shandong, China

Received:2022-01-21 Accepted:2022-02-22 Online:2022-12-18 Published:2022-10-18
Contact: Jintao Zhang
About author:First author contact:^†Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22175108);Natural Science Foundation of Shandong Province(ZR2020JQ09);Taishan Scholars Program of Shandong Province(tsqn20161004);Project for Scientific Research Innovation Team of Young Scholar in Colleges, Universities of Shandong Province(2019KJC025)

摘要/Abstract

摘要：

合理设计高效稳定的氧还原反应(ORR)和氧析出反应(OER)双功能电催化剂对于提升可充电锌-空气电池的能量密度和循环性至关重要. 为了降低对贵金属基催化剂的依赖, 过渡金属-碳基复合电催化剂引起了研究人员的广泛关注.

本文以植酸掺杂的聚苯胺为碳前驱体, 通过调节pH可控络合吸附钴离子, 在氨气气氛中一步热解获得了磷化钴纳米颗粒镶嵌的氮、磷共掺杂的三维多孔碳电催化剂. 三维多孔碳基底能够缓解高温热解引起的金属颗粒团聚、失活等问题, 原位形成的磷化钴纳米颗粒能够协同促进电催化ORR, OER, 析氢反应(HER)活性, 从而提高可充电锌-空气电池性能. 通过调节苯胺与植酸的投料比, 制备了短枝状(B-PANI-PA)和纤维状(F-PANI-PA)两种不同形貌的聚苯胺前驱体. 傅里叶变换红外光谱测试结果表明, 植酸成功掺杂至聚苯胺骨架中. 随后, 利用紫外-可见吸收光光谱研究了分散液pH对钴离子吸附量的影响. 将pH从4.0调至7.3后, 位于510 nm处归属于水合钴离子的吸收峰强度明显减弱, 表明其吸附钴离子的能力增强. X射线粉末衍射结果表明, 由两种不同的聚苯胺前驱体吸附钴离子后热解合成的磷化钴具有不同的暴露晶面, 均为CoP和CoP₃的混合相. 相比之下, 吸附更多钴离子的B-PANI-PA-Co-7.3样品则对应于Co₂P物相. 该形成过程主要归因于: 钴含量一定时, 在氨气还原性气氛中, 随时间的延长植酸热分解会逐步释放磷源, 从而形成富磷元素的磷化钴; 反之, 当钴过量时, 则更倾向于生成富钴元素的磷化钴. X射线光电子能谱结果再次验证了高温过程中磷化钴的原位形成和磷元素对碳基底的掺杂作用.

电催化氧还原反应性能测试表明, CoP_X@B-NPC催化剂展现出良好的半波电位(E_1/2 = 0.84 V vs. RHE), 高的动力学电流密度(5.2 mA cm^-2), 较好的四电子选择性, 较大的电化学活性面积(19.8 mF cm^-2). 以CoP_X@B-NPC作为空气电极催化剂组装的可充电液态电解质锌-空气电池展现出高达1.49 V的开路电压, 峰值功率密度可达到368 mW cm^-2, 高于商用Pt/C-RuO₂混合催化剂组装的电池(237 mW cm^-2). 在25.0 mA cm^-2的电流密度下, CoP_X@B-NPC组装的电池的比容量高达762 mAh g_Zn^-1. 长循环充放电测试中, 电池在260 h内没有明显的电压衰减. 值得注意的是, 以CoP_X@B-NPC组装的柔性固态电解质锌-空气电池的开路电压可达到1.48 V, 可与液态电解质锌-空气电池相媲美. 此外, CoP_X@B-NPC组装的电池在0.81 V下可达到峰值功率密度160 mW cm^-2. 在柔性测试中, 电池展现出良好的机械稳定性, 弯折时仍保持稳定的充放电循环性能. 由锌-空气电池驱动的水分解装置具有良好的产气效率, 体现了该催化剂的多效催化活性. 综上, 本文为发展高效、稳定的三维多孔碳基复合催化剂提供了一种方便有效的合成方法.

关键词: 磷化钴, 三维多孔碳, 电催化, 锌-空气电池, 水分解

Abstract:

The rational design of efficient and stable carbon-based electrocatalysts for oxygen reduction and oxygen evolution reactions is crucial for improving energy density and long-term stability of rechargeable zinc-air batteries (ZABs). Herein, a general and controllable synthesis method was developed to prepare three-dimensional (3D) porous carbon composites embedded with diverse metal phosphide nanocrystallites by interfacial coordination of transition metal ions with phytic acid-doped polyaniline networks and subsequent pyrolysis. Phytic acid as the dopant of polyaniline provides favorable anchoring sites for metal ions owing to the coordination interaction. Specifically, adjusting the concentration of adsorbed cobalt ions can achieve the phase regulation of transition metal phosphides. Thus, with abundant cobalt phosphide nanoparticles and nitrogen- and phosphorus-doping sites, the obtained carbon-based electrocatalysts exhibited efficient electrocatalytic activities toward oxygen reduction and evolution reactions. Consequently, the fabricated ZABs exhibited a high energy density, high power density of 368 mW cm^‒2, and good cycling/mechanical stability, which could power water splitting for integrated device fabrication with high gas yields.

Key words: Cobalt phosphide, Three-dimensional porous carbon, Electrocatalysis, Zinc-air battery, Water splitting.

舒欣欣, 杨茅茂, 刘苗苗, 王怀生, 张进涛. 三维多孔碳限域的磷化钴电催化剂用于高效的锌-空气电池和水分解[J]. 催化学报, 2022, 43(12): 3107-3115.

Xinxin Shu, Maomao Yang, Miaomiao Liu, Huaisheng Wang, Jintao Zhang. In-situ formation of cobalt phosphide nanoparticles confined in three-dimensional porous carbon for high-performing zinc-air battery and water splitting[J]. Chinese Journal of Catalysis, 2022, 43(12): 3107-3115.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)64047-0

https://www.cjcatal.com/CN/Y2022/V43/I12/3107

图/表 6

Scheme 1. Schematic illustration for the preparation of cobalt phosphide NPs embedded 3D porous carbon.

Fig. 1. Morphology and microstructure characterization. SEM and TEM images of B-NPC (a,b), CoPX@B-NPC (c,d) and CoPX@F-NPC (e,f). (g,h) HR-TEM images of CoPX@B-NPC. (i) STEM image and the corresponding elemental mapping images of CoPX@B-NPC.

Fig. 2. Characterization of electrocatalysts. (a) Nitrogen adsorption-desorption isotherms. (b) Pore distribution curves. (c) XRD patterns. High-resolution XPS spectra of CoPX@B-NPC: Co 2p region (d), P 2p region (e) and N 1s region (f).

Fig. 3. Electrocatalytic performance evaluation in alkaline electrolyte. (a) LSV curves for ORR. (b) Corresponding Tafel plots. (c) LSV curves on CoPX@B-NPC at different rotation rates and corresponding Koutechy?-Levich plots (inset). (d) Peroxide yield and electron transfer number derived from rotating ring-disk electrodes; LSV curves for OER in 1 mol L-1 KOH (e) and for bifunctional catalytic activity (f) in 0.1 mol L-1 KOH.

Fig. 4. ZAB performance evaluation. (a) Galvanostatic discharging curves. (b) Cathodic polarization curves and corresponding power density plots. (c) Specific capacity plots at various current densities using CoPX@B-NPC electrode; polarization curves (d) and galvanostatic cycling test (e) at current density of 5 mA cm?2.

Fig. 5. Solid-state ZAB performance. (a) Open-circuit voltage plots. (b) Galvanostatic discharging curves. (c) Polarization curves and corresponding power density curves. (d) Polarization curves. (e) Galvanostatic cycling test at a current density of 1 mA cm?2. (f) Galvanostatic cycling test under flat and bending conditions.

参考文献

[1]	X. Shu, M. Yang, D. Tan, K. S. Hui, K. N. Hui, J. Zhang, Mater. Adv., 2021, 2, 96-114.
[2]	M. Yang, X. Shu, W. Pan, J. Zhang, Small, 2021, 17, 2006773.
[3]	M. Yang, X. Shu, J. Zhang, ChemCatChem, 2020, 12, 4105-4111.
[4]	D. Tan, B. Wulan, X. Cao, J. Zhang, Nano Energy, 2021, 89, 106460.
[5]	Q. Chen, S. Chen, L. Zhao, J. Ma, H. Wang, J. Zhang, Chem. Eng. J., 2022, 431, 133961.
[6]	H. Li, X. Shu, P. Tong, J. Zhang, P. An, Z. Lv, H. Tian, J. Zhang, H. Xia, Small, 2021, 17, 2102002.
[7]	C. Guan, A. Sumboja, H. Wu, W. Ren, X. Liu, H. Zhang, Z. Liu, C. Cheng, S. J. Pennycook, J. Wang, Adv. Mater., 2017, 29, 1704117.
[8]	Z. Zhang, Y. P. Deng, Z. Xing, D. Luo, S. Sy, Z. P. Cano, G. Liu, Y. Jiang, Z. Chen, ACS Nano, 2019, 13, 7062-7072.
[9]	J. F. Callejas, C. G. Read, C. W. Roske, N. S. Lewis, R. E. Schaak, Chem. Mater., 2016, 28, 6017-6044.
[10]	W. Xu, S. Zhu, Y. Liang, Z. Cui, X. Yang, A. Inoue, J. Mater. Chem. A, 2018, 6, 5574-5579.
[11]	G. Yuan, D. Liu, X. Feng, M. Shao, Z. Hao, T. Sun, H. Yu, H. Ge, X. Zuo, Y. Zhang, Adv. Mater., 2021, 33, 108985.
[12]	Y. Li, S. Guo, T. Jin, Y. Wang, F. Cheng, L. Jiao, Nano Energy, 2019, 63, 103821.
[13]	S. H. Ahn, A. Manthiram, Small, 2017, 13, 1702068.
[14]	Y. Niu, M. Xiao, J. Zhu, T. Zeng, J. Li, W. Zhang, D. Su, A. Yu, Z. Chen, J. Mater. Chem. A, 2020, 8, 9177-9184.
[15]	X. Wang, W. Ma, Z. Xu, H. Wang, W. Fan, X. Zong, C. Li, Nano Energy, 2018, 48, 500-509.
[16]	M. Luo, W. Sun, B. B. Xu, H. Pan, Y. Jiang, Adv. Energy Mater., 2021, 11, 2002762.
[17]	L. Tang, X. Meng, D. Deng, X. Bao, Adv. Mater., 2019, 31, 1901996.
[18]	D. Ji, L. Fan, L. Li, S. Peng, D. Yu, J. Song, S. Ramakrishna, S. Guo, Adv. Mater., 2019, 31, 1808267.
[19]	K. Yuan, D. Lutzenkirchen-Hecht, L. Li, L. Shuai, Y. Li, R. Cao, M. Qiu, X. Zhuang, M. K. H. Leung, Y. Chen, U. Scherf, J. Am. Chem. Soc., 2020, 142, 2404-2412.
[20]	J. Zhang, Y. Zhao, C. Chen, Y. C. Huang, C. L. Dong, C. J. Chen, R. S. Liu, C. Wang, K. Yan, Y. Li, G. Wang, J. Am. Chem. Soc., 2019, 141, 20118-20126.
[21]	L. Zhu, D. Zheng, Z. Wang, X. Zheng, P. Fang, J. Zhu, M. Yu, Y. Tong, X. Lu, Adv. Mater., 2018, 30, 1805268.
[22]	S. Chen, L. Zhao, J. Ma, Y. Wang, L. Dai, J. Zhang, Nano Energy, 2019, 60, 536-544.
[23]	S. Chen, X. Shu, H. Wang, J. Zhang, J. Mater. Chem. A, 2019, 7, 19719-19727.
[24]	X. Chen, Z. Yan, M. Yu, H. Sun, F. Liu, Q. Zhang, F. Cheng, J. Chen, J. Mater. Chem. A, 2019, 7, 24868-24876.
[25]	F. Meng, H. Zhong, D. Bao, J. Yan, X. Zhang, J. Am. Chem. Soc., 2016, 138, 10226.
[26]	L. Pan, G. Yu, D. Zhai, H.R. Lee, W. Zhao, N. Liu, H. Wang, B. C. Tee, Y. Shi, Y. Cui, Z. Bao, Proc. Natl. Acad. Sci. U. S. A., 2012, 109, 9287-9292.
[27]	A. B. Jorge, R. Jervis, A. P. Periasamy, M. Qiao, J. Feng, L. N. Tran, M. M. Titirici, Adv. Energy Mater., 2020, 10, 1902494.
[28]	H. J. Kim, S. Im, J. C. Kim, W. G. Hong, K. Shin, H. Y. Jeong, Y. J. Hong, ACS Sustainable Chem. Eng., 2017, 5, 6654-6664.
[29]	X. Liu, M. Antonietti, Carbon, 2014, 69, 460-466.
[30]	N. Armaroli, V. Balzani, Angew. Chem. Int. Ed., 2007, 46, 52-66.
[31]	Q. Liu, J. Tian, W. Cui, P. Jiang, N. Cheng, A. M. Asiri, X. Sun, Angew. Chem. Int. Ed., 2014, 53, 6710-4.
[32]	N. Kornienko, N. Heidary, G. Cibin, E. Reisner, Chem. Sci., 2018, 9, 5322-5333.
[33]	X. Shu, S. Chen, S. Chen, W. Pan, J. Zhang, Carbon, 2020, 157, 234-243.
[34]	S. Zhou, J. Qin, X. Zhao, J. Yang, Chin. J. Catal., 2021, 42, 571-582.
[35]	F. Shi, X. Zhu, W. Yang, Chin. J. Catal., 2020, 41, 390-403.
[36]	K. Chen, S. Ci, Q. Xu, P. Cai, M. Li, L. Xiang, X. Hu, Z. Wen, Chin. J. Catal., 2020, 41, 858-867.

三维多孔碳限域的磷化钴电催化剂用于高效的锌-空气电池和水分解

In-situ formation of cobalt phosphide nanoparticles confined in three-dimensional porous carbon for high-performing zinc-air battery and water splitting

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 6

参考文献

相关文章 15

编辑推荐

Metrics

[1]	唐小龙, 李锋, 李方, 江燕斌, 余长林. 单原子催化剂在光催化和电催化合成过氧化氢中的研究进展[J]. 催化学报, 2023, 52(9): 79-98.
[2]	张季, 俞爱民, 孙成华. 非金属掺杂石墨烯异核双原子催化剂氮还原特性研究[J]. 催化学报, 2023, 52(9): 263-270.
[3]	胡金念, 田玲婵, 王海燕, 孟洋, 梁锦霞, 朱纯, 李隽. MXene负载3d金属单原子高效氮还原电催化剂的理论筛选[J]. 催化学报, 2023, 52(9): 252-262.
[4]	洪岩, 王琦, 阚子旺, 张禹烁, 郭晶, 李思琦, 刘松, 李斌. 电化学氮还原氨反应催化剂的最新研究进展[J]. 催化学报, 2023, 52(9): 50-78.
[5]	刘勇, 赵晓丽, 隆昶, 王晓艳, 邓邦为, 李康璐, 孙艳娟, 董帆. 原位构筑动态Cu/Ce(OH)_x界面用于高活性、高选择性和高稳定性硝酸盐还原合成氨[J]. 催化学报, 2023, 52(9): 196-206.
[6]	高晖, 张恭, 程东方, 王永涛, 赵静, 李晓芝, 杜晓伟, 赵志坚, 王拓, 张鹏, 巩金龙. 构建Cu台阶位促进电催化CO₂还原制醇类化学品的研究[J]. 催化学报, 2023, 52(9): 187-195.
[7]	邹心仪, 顾均. 酸性条件下二氧化碳高效电还原策略[J]. 催化学报, 2023, 52(9): 14-31.
[8]	赵磊, 张震, 朱昭昭, 李平波, 蒋金霞, 杨婷婷, 熊佩, 安旭光, 牛晓滨, 齐学强, 陈俊松, 吴睿. 缺陷氮掺杂碳耦合Co-N₅单原子位点用于高效锌-空气电池[J]. 催化学报, 2023, 51(8): 216-224.
[9]	乔蔚, 于立策, 常进法, 杨甫林, 冯立纲. MoSe₂纳米片耦合Pt纳米颗粒用于高效双功能催化甲醇辅助水电解制氢[J]. 催化学报, 2023, 51(8): 113-123.
[10]	周波, 石建巧, 姜一民, 肖磊, 逯宇轩, 董帆, 陈晨, 王特华, 王双印, 邹雨芹. 强化脱氢动力学实现超低电池电压和大电流密度下抗坏血酸电氧化[J]. 催化学报, 2023, 50(7): 372-380.
[11]	王元男, 王立娜, 张可新, 徐靖尧, 武倩楠, 谢周兵, 安伟, 梁宵, 邹晓新. 钙钛矿氧化物在水裂解反应中的电催化研究[J]. 催化学报, 2023, 50(7): 109-125.
[12]	周纳, 王家志, 张宁, 王志, 王恒国, 黄岗, 鲍迪, 钟海霞, 张新波. 富含缺陷的Cu@CuTCNQ复合材料增强电催化硝酸盐还原成氨[J]. 催化学报, 2023, 50(7): 324-333.
[13]	李轩, 蒋兴星, 孔艳, 孙建桔, 胡琪, 柴晓燕, 杨恒攀, 何传新. GaN/In₂O₃的界面工程用于高效电催化CO₂还原制备甲酸[J]. 催化学报, 2023, 50(7): 314-323.
[14]	Sang Eon Jun, Sungkyun Choi, Jaehyun Kim, Ki Chang Kwon, Sun Hwa Park, Ho Won Jang. 用于电化学能量转换反应的非贵金属单原子催化剂[J]. 催化学报, 2023, 50(7): 195-214.
[15]	牛青, 米林华, 陈玮, 李秋军, 钟升红, 于岩, 李留义. 基于共价有机框架的单位点光(电)催化材料的研究进展[J]. 催化学报, 2023, 50(7): 45-82.